This study demonstrates the effect of Cobalt substitution on the structure, ferroelectric, and magnetic properties of BiFeO3 (BFO) nanofibers. The BiFe1-xCoxO3 (x = 0, 0.05, 0.1) nanofibers were successfully synthesized by a sol-gel based electrospinning method followed by thermal treatment. The BiFe1-xCoxO3 nanofibers prepared under optimized conditions are a polycrystalline fiber that presents a rhombohedral distorted perovskite structure with a little amount impurity phase. Room temperature polarization and magnetization results indicated the multiferroic behavior of the nanofibers. Especially, the remnant magnetization is increased from 0.18 emu g(-1) to 1.72 emu g(-1) on increasing amount of Co substitution. The improvement of magnetism can be attributed to the Cobalt doping and size-effect.